Improvements in DFT Calculations of Spin–Spin Coupling Constants

Different types of spin–spin coupling constants (SSCCs) for several representative small molecules are evaluated and analyzed using a combination of 10 exchange functionals with 12 correlation functionals. For comparison, calculations performed using MCSCF, SOPPA, other common DFT methods, and also...

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Veröffentlicht in:Journal of chemical theory and computation 2014-11, Vol.10 (11), p.4938-4949
Hauptverfasser: Fabián, J. San, García de la Vega, J. M, San Fabián, E
Format: Artikel
Sprache:eng
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Zusammenfassung:Different types of spin–spin coupling constants (SSCCs) for several representative small molecules are evaluated and analyzed using a combination of 10 exchange functionals with 12 correlation functionals. For comparison, calculations performed using MCSCF, SOPPA, other common DFT methods, and also experimental data are considered. A detailed study of the percentage of Hartree–Fock exchange energy in SSCCs and in its four contributions is carried out. From the above analysis, a combined functional formed with local Slater (34%), Hartree–Fock exchange (66%), and P86 correlation functional (S66P86) is proposed in this paper. The accuracy of the values obtained with this hybrid functional (mean absolute deviation of 4.5 Hz) is similar to that of the SOPPA method (mean absolute deviation of 4.6 Hz).
ISSN:1549-9618
1549-9626
DOI:10.1021/ct500676m